JP2009034579A - Heat ray highly reflecting coated material and coating method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat ray reflective coated material capable of making stain inconspicuous and stably maintaining reflection performance of the heat ray and a coating method for forming the heat ray highly reflecting coated material. <P>SOLUTION: In the heat ray highly reflecting coated material, a coating material composition layer (A) which contains a composite metal oxide pigment containing oxide of Bi and/or Y and oxide of Mn and a resin (a) is formed on a material to be coated and a coating material composition layer (B) which contains a compound expressed by a general formula Si(OR)<SB>4</SB>(in the formula, R can be the same as or different from each other and each expresses hydrogen atom or a 1-5C alkyl group) or the partially condensed material and a resin (b) is formed on the coating material composition layer (A). The coating method includes: applying a specific composition on the material to be coated to form the coating material composition layer (A) and applying a specific composition on the coating material composition layer (A) to form the coating material composition layer (B). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a heat ray high-reflective coating that can be applied to objects to be coated such as roofs, roofs and outer walls of buildings, vehicles, ships, plants, storerooms, roads, and the like, and a method for coating the heat-reflective coating.

In general, dark paints containing black pigments are often used on the roofs of buildings. However, dark color paints generally have a problem that they easily absorb solar energy, increase the temperature of buildings and the like, and increase energy consumption for air conditioning.
On the other hand, although white-colored coating films can be expected to be highly reflective of heat rays, they have the problem of landscape that contamination is conspicuous, and the reflection performance of heat rays deteriorates due to contamination.

In order to solve this problem, Patent Documents 1 and 2 disclose a paint composition colored in black, which is an achromatic color, by mixing chromatic pigments of red, orange, yellow, green, blue, and purple. Proposed. However, it is difficult to adjust the color tone, and the color pigment is deteriorated by ultraviolet rays, so that it is liable to change color.
Further, as an example using a heat ray high reflection pigment, Patent Document 3 proposes a black fired pigment coating composition having a high solar radiation reflectance in the near infrared region. However, since chromium-based pigments are used, there is a problem that the health of workers during painting work is impaired and the environment is polluted.
Further, as dark-colored heat ray high reflection pigments, pigments containing bismuth manganese oxide (Patent Document 4) and pigments containing rare earth manganese oxide (Patent Document 5) have been proposed.
Japanese Patent No. 2593968 JP-A-5-293434 Japanese Patent No. 3468698 JP-T-2002-532379 JP 2002-38048 A

In consideration of the effects on the health and environment of workers, the present inventors have used a complex metal oxide containing a Bi and / or Y oxide and a Mn oxide as a dark-colored heat ray highly reflective pigment. We considered using pigments.
However, it has been found that the coating film using the composite metal oxide pigment has a problem that the reflective performance of the heat ray is lowered with time.
The present invention has been made in view of the above circumstances, and includes a composite metal oxide pigment containing an oxide of Bi and / or Y and an oxide of Mn, hardly contaminating, and heat ray reflection performance. It is an object of the present invention to provide a highly heat-reflective coated product that can stably maintain the coating, and a coating method for forming the heat-reflective coated product.

The heat ray highly reflective coated article of the present invention has a paint composition layer (A) on the article to be coated and a paint composition layer (B) formed on the paint composition layer (A). It is. The coating composition layer (A) contains a composite metal oxide pigment containing an oxide of Bi and / or Y and an oxide of Mn, and a resin (a), and the coating composition layer (B) Is a compound represented by the general formula Si (OR) ₄ (wherein R may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) or a partial condensate thereof; It contains a resin (b).

  In the heat ray highly reflective coating of the present invention, the coating composition layer (B) preferably further contains an ultraviolet absorber. Moreover, it is preferable that a part or all of the resin (a) and / or the resin (b) is a fluororesin. Moreover, it is preferable that content of the composite metal oxide pigment contained in the said coating composition layer (A) is 0.1 mass% or more with respect to the total amount of a composite metal oxide pigment and resin (a). . Moreover, it is preferable that the said coating composition layer (A) and / or the said coating composition layer (B) contain a hardening | curing agent further.

Moreover, the coating method of the heat ray highly reflective coating of the present invention comprises a composite metal oxide pigment containing Bi and / or Y oxide and Mn oxide on a workpiece, and a resin (a). The coating composition layer (A) is formed by applying the composition (A1) containing, and then the general formula Si (OR) ₄ (wherein R is the same as each other) on the coating composition layer (A). However, it may be different, and represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.) A composition (B1) containing a compound represented by the above or a partial condensate thereof and a resin (b) It is a method characterized by forming a composition layer (B).

  In the coating method of the heat ray highly reflective coating of the present invention, it is preferable that the composition (B1) further contains an ultraviolet absorber. Moreover, it is preferable that a part or all of the resin (a) and / or the resin (b) is a fluororesin. Moreover, it is preferable that content of the composite metal oxide pigment contained in the said composition (A1) is 0.1 mass% or more with respect to the total amount of a composite metal oxide pigment and resin (a). Moreover, it is preferable that the said composition (A1) and / or the said composition (B1) contain the hardening | curing agent further.

The heat ray highly reflective coating of the present invention is less susceptible to contamination and can stably maintain the heat ray reflection performance.
Moreover, according to the coating method of the present invention, it is possible to form a highly heat-reflective coated product that is less likely to be contaminated and that can stably maintain the heat ray reflection performance.

<High heat reflective coating>
The heat ray highly reflective coating product of the present invention (hereinafter referred to as the present coating product) comprises a coating composition layer (A) and a coating composition formed on the coating composition layer (A). A layer (B).

[To be painted]
The material to be coated is not particularly limited. For example, inorganic materials such as concrete, natural stone, and glass; metals such as iron, stainless steel, aluminum, copper, brass, and titanium; wood; synthetic organic materials such as plastic and rubber The object to be coated is made up of. Other coating films and adhesive layers may be formed on the surface of the object to be coated. The material of the object to be coated may be fiber reinforced plastic, resin reinforced concrete, fiber reinforced concrete, or the like, which is an organic-inorganic composite material.

  The object to be painted may be movable or real estate. For example, industrial equipment such as automobiles, trains, aircraft and other transportation equipment, bridge members, steel towers, civil engineering members, waterproof sheets, tanks, pipes, etc. Building exteriors, doors, window gate members, monuments, poles and other building components, road median strips, road components such as guardrails, communication equipment, electrical and electronic components, buildings, chemical plants, chimneys, bridges, etc. Examples include buildings.

[Coating composition layer (A)]
The coating composition layer (A) is a layer formed on the object to be coated, and is usually a layer formed on a part or all of one surface of the surface of the object to be coated. The coating composition layer (A) is usually formed on the surface of the article to be irradiated with sunlight. The coating composition layer (A) is preferably formed on the surface of the object to be coated, directly or via a layer formed by pretreatment such as primer treatment or application of a primer, Usually, the latter is preferred. That is, it is preferable that the coating composition layer (A) is formed on the surface subjected to the pretreatment on the surface of the object to be coated.
The coating composition layer (A) contains a composite metal oxide pigment (hereinafter referred to as “composite pigment M”) containing an oxide of Bi and / or Y and an oxide of Mn, and a resin (a). A layer is formed on an object to be coated.

(Composite Pigment M)
The composite pigment M contains an oxide of Bi and / or Y and an oxide of Mn.
The composite pigment M in the present invention contains any one or more selected from Bi oxide, Y oxide and Mn oxide, Bi oxide and Mn oxide, and Y oxide and Mn oxide.
The content of manganese in the composite pigment M is preferably 5 to 65% by mass, and more preferably 10 to 50% by mass. If the manganese content is low, the heat reflection effect may not be sufficiently obtained.
As the composite pigment M, it is preferable to use a mixture obtained by baking a mixture of Bi and / or Y and Mn at a baking temperature of 700 ° C. or higher. The average particle size of the composite pigment M is preferably 0.1 μm to 30 μm. If the average particle size is too large, the gloss may be lowered. Examples of commercially available products that satisfy these preferred conditions include Asahi Kasei Kogyo Co., Ltd. Black 6303, Black 6301, and the like.

The composite pigment M is a black-colored pigment, and can be mixed and dispersed in a resin.
The content of the composite pigment M is 0.1 to 200% by mass with respect to the total amount of the composite pigment M and the resin (a) when only the composite pigment M is used as the pigment in the coating composition layer (A). It is preferably 10 to 200% by mass. When the content of the composite pigment M is small, the heat reflection effect cannot be sufficiently obtained. On the other hand, when there is too much content, there exists a possibility that glossiness may fall.

The coating composition layer (A) may contain other color pigments in order to adjust the color tone according to the application and purpose. For example, inorganic pigments such as titanium oxide, brown rice, ocher, calcium carbonate, aluminum silicate, white carbon, finely divided silicic acid, and organic pigments such as phthalocyanine blue, phthalocyanine green, quinacridone, isoindolinone, benzimidazolone and dioxazine. Can be used.
Since this coated product often has a dark color tone, it is preferable to adjust the pigment composition to a dark color tone. Specifically, the lightness L ^* defined in JIS Z 8729 on the surface of the coated product is preferably 5 to 80, and more preferably 10 to 60.

  The content of the entire pigment is preferably 0.1 to 200% by mass and more preferably 10 to 100% by mass with respect to the total amount of the entire pigment and the resin (a) described later. When the content of the entire pigment is small, the content of the composite pigment M decreases, and the heat reflection effect cannot be obtained sufficiently. On the other hand, if the content of the entire pigment is too large, the gloss may be lowered.

(Resin (a))
The coating composition layer (A) contains the composite pigment M and the resin (a).
As resin (a), it is preferable that the one part or all part is a fluororesin. By using the fluororesin, the coating composition layer (A) having good weather resistance is formed.
As the fluororesin, a fluoroolefin copolymer is preferable. The fluoroolefin copolymer is a copolymer of a fluoroolefin and another copolymerizable monomer copolymerizable with the fluoroolefin. Another copolymerizable monomer may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the fluoroolefin composing the fluoroolefin copolymer include C2-C3 fluoroolefins such as tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, vinylidene fluoride, and vinyl fluoride.
The proportion of the polymer units based on the fluoroolefin in the fluoroolefin copolymer is preferably 20 to 70 mol% from the viewpoint of obtaining sufficient weather resistance.

  As another copolymerizable monomer constituting the fluoroolefin copolymer, a vinyl monomer, that is, a compound having a carbon-carbon double bond is preferable. Examples of vinyl monomers include vinyl ether, allyl ether, carboxylic acid vinyl ester, carboxylic acid allyl ester, and olefin.

Examples of the vinyl ether include cycloalkyl vinyl ethers such as cyclohexyl vinyl ether; alkyl vinyl ethers such as nonyl vinyl ether, 2-ethylhexyl vinyl ether, hexyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, and t-butyl vinyl ether.
Examples of allyl ethers include alkyl allyl ethers such as ethyl allyl ether and hexyl allyl ether.

Examples of the carboxylic acid vinyl ester or the carboxylic acid allyl ester include vinyl esters or allyl esters of carboxylic acids such as acetic acid, butyric acid, pivalic acid, benzoic acid, and propionic acid. As the carboxylic acid vinyl ester, commercially available products such as Veova-9 and Veova-10 (both manufactured by Shell Chemical Co., Ltd.) may be used as vinyl esters of carboxylic acids having a branched alkyl group.
Examples of olefins include ethylene, propylene, and isobutylene.

  Further, the fluoroolefin copolymer is preferably a fluoroolefin copolymer having a functional group capable of forming a crosslink by reacting with a curing agent described later. The type of the functional group can be appropriately selected depending on the combination with the curing agent. Representative examples include a hydroxyl group, a carboxy group, a hydrolyzable silyl group, an epoxy group, and an amino group.

Examples of the method for introducing a functional group include a method of copolymerizing a monomer having a functional group, or a method of introducing a functional group by a reaction after polymerization.
Examples of the monomer having a functional group include the following.
Hydroxyalkyl vinyl ethers such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether and cyclohexanediol monovinyl ether, which are monomers having a hydroxyl group; hydroxyalkyl allyl ethers such as 2-hydroxyethyl allyl ether; or vinyl hydroxyalkyl crotonates Vinyl ester or allyl ester of hydroxyl group-containing carboxylic acid. Crotonic acid, undecenoic acid, etc., which are monomers having a carboxy group. Triethoxyvinylsilane, which is a monomer having a hydrolyzable silyl group. Glycidyl vinyl ether, glycidyl allyl ether, etc., which are monomers having an epoxy group. Aminopropyl vinyl ether, aminopropyl vinyl ether, etc., which are monomers having an amino group.

  As a method for introducing a functional group by a reaction after polymerization, for example, a method in which a hydroxyl group is introduced by saponifying a polymer copolymerized with a carboxylic acid vinyl ester, a polyvalent carboxylic acid or its anhydride is added to a polymer having a hydroxyl group. Of introducing a carboxy group by reacting a product, a method of introducing a hydrolyzable silyl group by reacting an isocyanate alkylalkoxysilane with a polymer having a hydroxyl group, and reacting a polyvalent isocyanate compound with a polymer having a hydroxyl group. Examples thereof include a method for introducing an isocyanate group.

  Preferable specific examples of the fluoroolefin copolymer include, for example, chlorotrifluoroethylene, cyclohexyl vinyl ether, copolymer of alkyl vinyl ether and hydroxyalkyl vinyl ether, copolymer of chlorotrifluoroethylene, alkyl vinyl ether and allyl alcohol, chloro Examples thereof include a copolymer of trifluoroethylene, an aliphatic carboxylic acid vinyl ester and a hydroxyalkyl vinyl ether, or a copolymer using tetrafluoroethylene in place of chlorotrifluoroethylene in these copolymers. As these copolymers, commercially available products such as Lumiflon (Asahi Glass) and Cefral Coat (Central Glass) can be used.

  A fluoroolefin type copolymer may be used individually by 1 type, and may be used in combination of 2 or more type. The number average molecular weight of the fluoroolefin copolymer is preferably 2,000 to 100,000, and more preferably 6,000 to 30,000.

  When a fluororesin is used as the resin (a), a fluororesin other than the fluoroolefin copolymer may be used alone or together with the fluoroolefin copolymer. Resins (a) other than fluororesins include alkyd resins, amino alkyd resins, polyester resins, epoxy resins, urethane resins, epoxy polyester resins, polyvinyl acetate resins, acrylic resins, vinyl chloride resins, phenol resins, and silicone-modified resins. A polyester resin, an acrylic silicone resin, a silicone resin, etc. are mentioned, These may be used independently as a resin (a), or may be used with a fluororesin.

(Curing agent)
When resin (a) contains the copolymer which has a functional group, it is preferable to contain a hardening | curing agent. As the curing agent, various curing agents known as coating curing agents can be used. Specific examples of the curing agent include amino-based curing agents such as aminoplasts and urea resins, polyvalent isocyanate-based curing agents, and block polyvalent isocyanate-based curing agents. In the case of using a room temperature curing type curing agent, it is preferably blended before coating, and the blending time in the case of using a thermosetting type curing agent is not limited.
A hardening | curing agent may be used individually by 1 type, and may be used in combination of 2 or more type. However, when a self-curing resin is used as the resin (a), a curing agent may not be used.
The amount of the curing agent is determined based on the total number of moles of the curing group of the curing agent (hereinafter referred to as the number of moles of curing group) and the total number of moles of the functional group of the fluoroolefin copolymer having a functional group (hereinafter referred to as the number of moles of functional group) (The number of moles of curing group) / (number of moles of functional group), and the ratio value is hereinafter referred to as the total number of crosslinking points) is preferably 0.3 or more. It is particularly preferable to set it to 7 or more. By setting the total number of crosslinking points to 0.7 or more, the coating composition is cured well and a coating film excellent in solvent resistance can be obtained. The upper limit of the total number of cross-linking points is not particularly limited, but in consideration of the influence on the weather resistance and other performance due to the remaining reactive groups such as unreacted isocyanate groups in the coating film, 2.0 or less is Preferably, 1.3 or less is more preferable.

(Other ingredients)
The coating composition layer (A) may contain fine particle fillers, additives, and the like, if necessary.
As the fine particle filler, a hollow sphere that can impart heat insulation is generally used.
As the hollow sphere, an inorganic balloon, a resin balloon or the like is known depending on the material. Specific examples include glass balloons, shirasu balloons, alumina balloons, zirconia balloons, and aluminosilicate balloons.
The additive is not particularly limited, and examples thereof include matting agents such as silica and alumina, antifoaming agents, leveling agents, sagging inhibitors, surface conditioners, viscosity modifiers, dispersants, light stabilizers, curing catalysts, and the like. Conventional additives may be mentioned.

The thickness of the coating composition layer (A) is not particularly limited, is preferably 5 to 100 μm, and more preferably 20 to 50 μm.
When the thickness of the coating composition layer (A) is reduced, concealability and weather resistance tend to be reduced, and when the thickness is increased, construction problems such as sagging tend to occur.

[Coating composition layer (B)]
The coating composition layer (B) is a compound represented by the general formula Si (OR) ₄ (wherein R may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). Or it is the layer containing the partial condensate (henceforth "compound X") and resin (b).
The coating composition layer (B) is formed on the coating composition layer (A). On the coating composition layer (B), another layer may be provided as long as it does not interfere with the heat ray reflection performance of the present paint and the effect of maintaining the reflection performance and the effect of maintaining the beauty. However, the coating composition layer (B) is usually formed as the uppermost layer. By providing the coating composition layer (B) as the uppermost layer, the effect of preventing the contamination of the surface by the compound X and maintaining the aesthetic appearance becomes remarkable.

(Compound X)
Compound X contained in the coating composition layer (B) is a component that prevents contamination of the surface of the present paint and contributes to maintaining the heat ray reflection performance of the composite pigment M in a stable manner.

If the carbon number of R in the general formula exceeds 5, the effect of maintaining the heat ray reflection performance tends to decrease, so the carbon number of R is 1-5. R is preferably an alkyl group having 1 or 2 carbon atoms because a particularly excellent heat ray reflection performance maintaining effect is obtained. Particularly preferred compound X is tetramethoxysilane, tetraethoxysilane, or a partial condensate thereof.
Compound X preferably has a silica content of 20 to 60% by mass. If the silica content is too small, the effect of maintaining the heat ray reflection performance is lowered, and if it is too much, the storage stability is impaired. The silica content is a ratio of the silica (SiO ₂ ) obtained when the compound X undergoes 100% hydrolysis condensation with respect to the compound X.

The content of the compound X with respect to the solid content of the resin (b) is preferably 0.5 to 60% by mass, and more preferably 2 to 30% by mass. If the content of the compound X is too small, the effect of maintaining the heat ray reflection performance is lowered, and if it is too much, foam, sagging, leveling, etc. may occur and the paintability may be inferior.
In order to increase the proportion of silica, the composition (B1) for forming the layer (B) described later contains an accelerator for promoting dealkoxy group reaction of the compound X and reticulation of the molecule. Is preferred. Examples of the accelerator include conventionally known acidic catalysts such as hydrochloric acid and p-toluenesulfonic acid, and metal chelate compounds such as aluminum chelate.

  Compound X improves the stain resistance of the coating composition layer (B) by imparting hydrophilicity to the coating composition layer (B). And it is thought that an improvement in stain resistance prevents a decrease in the heat ray reflection performance of the composite pigment M contained in the coating composition layer (A). It was unexpected that the heat ray reflection performance when the composite pigment M, which is a black pigment, was used was maintained due to the stain resistance effect of the compound X.

(Resin (b))
The coating composition layer (B) contains the resin (b) together with the compound X. As an example of resin (b), the same thing as resin (a) is mentioned, A preferable aspect is also the same.
That is, part or all of the resin (b) is preferably a fluororesin. By using the fluororesin, the coating composition layer (B) having good weather resistance is formed. The resin (b) may be the same resin as the resin (a) or a different resin, regardless of whether a fluororesin or a resin other than a fluororesin is used. It is preferable to use it.

(UV absorber)
The coating composition layer (B) preferably further contains an ultraviolet absorber. The ultraviolet absorber suppresses deterioration of the composite pigment M due to ultraviolet rays, and suppresses a decrease in heat ray reflection performance.
Examples of the ultraviolet absorber include benzotriazole-based, cyanoacrylate-based, benzophenone-based, hydroxyphenyltriazine-based, and oxalic anilide-based ultraviolet absorbers.

0.1-20 mass% is preferable with respect to the total amount of a coating composition layer (B), and, as for content of the ultraviolet absorber in a coating composition layer (B), 0.5-10 mass% is more preferable.
If the amount of the ultraviolet absorber is increased, the effect of preventing the deterioration of the composite pigment M is enhanced. However, if the amount is too large, problems such as coloring of the coating film and softening of the coating film may occur. On the other hand, if the amount of the ultraviolet absorber is too small, the effect of preventing the deterioration of the composite pigment M may not be obtained sufficiently.
(Curing agent and other ingredients)
Moreover, it is preferable that a coating composition layer (B) contains a hardening | curing agent further. As the curing agent, the same curing agent as mentioned in the coating composition layer (A) can be used. A hardening | curing agent may be used individually by 1 type, and may be used in combination of 2 or more type. When a self-curing resin is used as the resin (b), a curing agent may not be used.
Moreover, the coating composition layer (B) may contain a fine filler, an additive, etc. as needed. These can use the thing similar to what was illustrated by the coating composition layer (A).

5-100 micrometers is preferable and, as for the thickness of a coating composition layer (B), 10-40 micrometers is more preferable.
When the thickness of the coating composition layer (B) is reduced, concealability and weather resistance tend to be reduced, and when the thickness is increased, construction problems such as sagging tend to occur.

[Intermediate layer (C)]
The present coated product does not hinder the heat ray reflection performance of the present coated product between the coating composition layer (A) and the coating composition layer (B), the effect of maintaining the reflective performance, and the effect of maintaining the aesthetic appearance. Another intermediate layer (C) may be provided within the range. However, it is preferable that the coating composition layer (B) is usually formed on the surface of the coating composition layer (A) and the intermediate layer (C) is not provided.

<Coating method>
In the coating method of the heat ray highly reflective coating of the present invention, the composition (A1) is applied on the object to be coated to form the coating composition layer (A), and then the composition (B1) is coated with the coating composition. It is a method characterized in that the coating composition layer (B) is formed by coating on the layer (A).
The composition (A1) is a coating composition for forming the coating composition layer (A), and the composition (B1) is a coating composition for forming the coating composition layer (B). ) And (B) are coating compositions containing each essential component.

The composition (A1) and the composition (B1) are preferably liquid compositions, and examples thereof include non-aqueous solvent-type paints, aqueous paints, and non-aqueous emulsion-type paints.
Examples of the solvent when the compositions (A1) and (B1) include a solvent include those that can be generally used as a solvent for paints, such as toluene, xylene, ExxonMobil Solvesso 100, ExxonMobil Solvesso 150, and the like. And petroleum petroleum mixed solvents; aromatic hydrocarbons such as mineral spirits; esters such as ethyl acetate and butyl acetate; ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; and water. These may be used alone or in combination of two or more.
When using a solvent, it is preferable to use a solvent composition in which the resins contained in the compositions (A1) and (B1) are dissolved or dispersed in a solvent.

  Although there is no limitation on the blending order of each component of the composition (A1), a method of adding a curing agent to the solvent composition in advance when adding a curing agent is preferred. Also, when adding additives such as matting agents, antifoaming agents, leveling agents, anti-sagging agents, surface conditioners, viscosity modifiers, dispersants, light stabilizers, curing catalysts, etc., a solvent composition together with the pigment It is preferable to mix them.

  Although there is no limitation on the blending order of each component of the composition (B1), when the accelerator of compound X is added, it is preferable to add the accelerator to compound X in advance. In addition, when the time from application of Compound X to the solvent composition to application is long, it is preferable to add an accelerator immediately before application of the composition (B1).

  There is no limitation on the curing method of the composition (A1) and the composition (B1), and various curing methods such as a thermosetting type, a thermoplastic type, a room temperature drying type, and a room temperature curing type can be used.

  When the composition (A1) is applied to the object to be coated, pre-treatment that is usually used when applying a paint, such as surface polishing, sanding treatment, sealing treatment, primer treatment, and application of a primer is performed. It is preferable. The kind of pre-treatment may be one kind or two or more kinds, and the number of times of each treatment may be once or twice or more. The sealing agent, primer, and undercoat used here are not particularly limited and include organic solvent solutions, non-aqueous dispersions, aqueous solutions, and aqueous dispersions.

  Examples of the primer or primer include epoxy resin-based, modified epoxy ester resin-based, vinyl resin-based, chlorinated rubber-based paints, and zinc phosphate, red lead, zinc powder, lead oxide as necessary. , Anticorrosive pigments such as calcium leadate, lead cyanamide, basic lead chromate, and basic lead sulfate, and scaly pigments such as iron oxide, mica, aluminum, and glass flakes. Moreover, in order to improve rust prevention power, a zinc rich primer may be used, and two or more kinds of the above-mentioned undercoat materials can be applied repeatedly.

  Various methods can be applied to the method of applying the composition (A1) and the composition (B1). For example, brush coating, spray coating, dipping method, roll coater or flow coater can be applied. In general, the composition (A1) and the composition (B1) are applied after the composition (A1) is applied and dried to form the coating composition layer (A). This is done by applying. Moreover, when forming an intermediate | middle layer (C), intermediate | middle layer (C) is formed by methods, such as application | coating, as needed before application | coating of a composition (B1). Application of the composition (B1) may be performed before the composition (A1) (intermediate layer (C)) is completely dried. The application of the composition (A1) and the composition (B1) may be performed once or more. The method of performing the coating a plurality of times is preferable as a method of increasing the film thickness without causing sagging.

The heat ray highly reflective coating of the present invention has a coating composition layer (A) containing the composite pigment M and a coating composition layer (B) containing the compound X, so that contamination is not noticeable, and Reflective performance can be maintained stably.
In the present invention, the composite pigment M is separately contained in the coating composition layer (A) and the compound X is separately contained in the coating composition layer (B), and the coating composition layer (B) is formed on the coating composition layer (A). Let Therefore, the surface contamination preventing effect by the compound X is further improved, and the deterioration of the composite pigment M is further suppressed. In addition, the heat ray highly reflective coated product of the present invention has a particularly high effect of maintaining the aesthetics by preventing contamination of the surface and maintaining the heat ray reflection performance by providing the coating composition layer (B) as the uppermost layer. Become.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated in detail, this invention is not limited by these description.
(Base material)
As the base material, an aluminum plate 140 mm × 240 mm × 0.5 mm subjected to a chromate treatment and an undercoating agent and an intermediate coating agent were sequentially applied.
As the undercoat, Bon Epocoat 55MP-S, gray (Asahi Glass Coat and Resin, Epoxy paint) was used. As an intermediate coating agent, Bonflon # 1000 white (Asahi Glass Coat and Resin Co., Ltd., fluorine paint) was used.

(Main agent 1: Preparation example of composition A1)
Fluororesin Lumiflon LF-200, a copolymer of chlorotrifluoroethylene, cyclohexyl vinyl ether, ethyl vinyl ether and hydroxyalkyl vinyl ether [manufactured by Asahi Glass Co., Ltd., hydroxyl group-containing fluoroolefin copolymer (hydroxyl value: 52 mgKOH / g) 60 mass% 15.0 g of xylene was added to 63.0 g.
Next, 22.0 g of black 6301 (manufactured by Asahi Kasei Kogyo Co., Ltd., Mn and Bi composite oxide pigment, manganese content 29 mass%) was added and dispersed by a sand mill. Further, a main agent 1 was prepared by adding 0.0005 g of dibutyltin dilaurate as a urethanization catalyst and stirring the mixture.

(Main agent 2: Preparation example of composition A1)
16.0 g of xylene was added to 63.0 g of fluororesin Lumiflon LF-200. Next, 21.0 g of black 6303 (manufactured by Asahi Kasei Kogyo Co., Ltd., composite oxide pigment of Mn and Y, manganese content 29% by mass) was added and dispersed by a sand mill. Furthermore, what added 0.0005g of dibutyltin dilaurate and stirred was used as the main ingredient 2.

(Main agent 3)
Xylene 34.0g was added to 63.0g of fluororesin Lumiflon LF-200. Next, 3.0 g of Mitsubishi Carbon Black MA-11 (Mitsubishi Chemical Corporation) was added and dispersed with a sand mill. Further, 0.0005 g of dibutyltin dilaurate was added and stirred, and the main agent 3 was used.

(Main agent 4)
63.0 g of fluororesin Lumiflon LF-200, 34.0 g of xylene and 3.0 g of UV absorber (Viosorb 910, manufactured by Kyodo Yakuhin Co., Ltd.) were added, and 0.0005 g of dibutyltin dilaurate was further added and stirred. It was.

(Composition 1: Preparation Example of Composition B1)
1.7g of aluminum chelate D (manufactured by Kawaken Fine Chemicals Co., Ltd., aluminum chelate compound) is added to 30.0g of Coronate HX (Nippon Polyurethane, non-yellowing type isocyanate curing agent) and mixed. Composition 1 was prepared by adding 17.0 g of silicate MS56S [Mitsubishi Chemical Co., Ltd., methyl silicate condensate having a silica content of 56 mass%] and mixing them.
(Composition 2)
Composition 2 was prepared by adding 18.7 g of xylene to 30.0 g of Coronate HX.

Hereinafter, examples, reference examples, and comparative examples will be described.
Example 1
12 g of the composition 2 was mixed with 100 g of the main agent 1 (59.8 g as a solid content), and coated on the substrate with a bar coater so as to have a film thickness of 30 μm. Then, the coating composition layer (A) was formed by curing for one day at a temperature of 23 ° C. and a relative humidity of 60%. Thereafter, 12 g of the composition 1 was further mixed with 100 g of the main agent 4 and applied to the coating composition layer (A) by spray coating so as to have a film thickness of 20 μm, and 7% at a temperature of 23 ° C. and a relative humidity of 60%. The coating composition layer (B) was formed by performing curing for a day, and the test body of Example 1 was obtained.
(Reference Example 1)
A coating composition obtained by mixing 12 g of the composition 1 with 100 g of the main agent 1 (59.8 g as a solid content) was applied on a substrate with a bar coater so as to have a film thickness of 30 μm. Thereafter, curing was carried out at a temperature of 23 ° C. and a relative humidity of 60% for 7 days to obtain a specimen of Reference Example 1.

(Example 2)
12 g of the composition 2 was mixed with 100 g of the main agent 2 (59.8 g as a solid content), and coated on the substrate with a bar coater so as to have a film thickness of 30 μm. Then, the coating composition layer (A) was formed by curing for one day at a temperature of 23 ° C. and a relative humidity of 60%. Thereafter, 12 g of the composition 1 was further mixed with 100 g of the main agent 4 and applied to the coating composition layer (A) by spray coating so as to have a film thickness of 20 μm, at a temperature of 23 ° C. and a relative humidity of 60%. A coating composition layer (B) was formed by curing for 7 days to obtain a test sample of Example 2.
(Reference Example 2)
A coating composition obtained by mixing 12 g of the composition 1 with 100 g of the main agent 2 (59.8 g as a solid content) was applied on a substrate with a bar coater so as to have a film thickness of 30 μm. Thereafter, curing was performed for 7 days at a temperature of 23 ° C. and a relative humidity of 60% to obtain a test sample of Reference Example 2.

(Comparative Example 1)
A coating composition obtained by mixing 12 g of composition 2 with 100 g of main agent 3 (40.8 g as a solid content) was applied on a substrate with a bar coater so as to have a film thickness of 30 μm. Thereafter, curing was performed at a temperature of 23 ° C. and a relative humidity of 60% for 7 days to obtain a specimen of Comparative Example 1.

(Comparative Example 2)
A coating composition obtained by mixing 12 g of the composition 2 with 100 g of the main agent 1 (59.8 g as a solid content) was applied on a substrate with a bar coater so as to have a film thickness of 30 μm. Thereafter, curing was performed for 7 days at a temperature of 23 ° C. and a relative humidity of 60% to obtain a test sample of Comparative Example 2.

(Comparative Example 3)
A coating composition obtained by mixing 12 g of the composition 2 with 100 g of the main agent 2 (59.8 g as a solid content) was applied on a substrate with a bar coater so as to have a film thickness of 30 μm. Thereafter, curing was performed for 7 days at a temperature of 23 ° C. and a relative humidity of 60%, to obtain a specimen of Comparative Example 3.

(Measurement of brightness)
About the surface of each test body, the lightness L ^* prescribed | regulated to JISZ8729 was measured using the spectrocolorimeter CM-2002 type | mold (Minolta company make). Since the brightness value of Example 1 is considered to be almost the same as the brightness value of Reference Example 1, the value measured in Reference Example 1 was used. Similarly, the value measured in Reference Example 2 was used as the brightness value of Example 2.

(Measurement of the initial temperature _{T 1)}
About each test body, the temperature of the test body surface when an infrared lamp was irradiated for 10 minutes was measured in the following procedures.
First, the thermocouple was installed in the center part of the test body surface. In addition, an infrared lamp was installed 60 cm from the surface of the test body. The infrared lamp was turned on for 10 minutes and then turned off.
The surface temperature of the specimen was continuously measured with a thermocouple for 15 minutes from the start of lighting of the infrared lamp to 5 minutes after the light was turned off. The highest temperature obtained in the course of the 15 minutes was the initial temperature T _1.

(Measurement of pollution after the temperature _{T 2)}
For each test specimen, as shown in the following procedure, after carrying out accelerated soil adhesion according to the Civil Engineering Research Center Method (Anti-fouling material evaluation promotion test method I) anti-fouling test, the post-contamination temperature T _{2 is set} to It was measured.
(1) As a soiling substance, 95% by mass of deionized water was mixed well with 5% by mass of carbon black for pigment (manufactured by Deggsa, particle size 0.002 to 0.028 μm) to prepare a suspension.
(2) About 1/3 of the suspension volume was added to the suspension, and glass beads (2 mmφ) were added and stirred at 2500 rpm using a stirrer. Thereafter, the glass beads were removed to separate the carbon black suspension.
(3) About 200 g / m ² of the carbon black suspension was sprayed on the surface of the test body. After spraying, it was baked and dried with a dryer at 60 ° C. for 1 hour.
(4) After cooling to room temperature, the gauze was moved in the vertical, horizontal and vertical order on the surface of the test specimen under running tap water, and the soiled substances were washed off lightly.
(5) Then, it dried at room temperature and obtained the soil test body.
(6) Test body, except that instead of the dirty specimen, in the same manner as in the measurement of the initial temperature T _1, obtains the highest temperature obtained in the course of 15 minutes, was contaminated after the temperature T _2.
Since the values of T ₁ and T ₂ in Example 1 are considered to be substantially the same as those in Reference Example 1, the values measured in Reference Example 1 were used. Similarly, the value measured in Reference Example 2 was used as the value in Example 2.

(Accelerated weather resistance test)
About each test body of an Example and a comparative example, the accelerated weather resistance test (1500 hours) using type 1 UVB313 described in the accelerated weather resistance test (ultraviolet fluorescent lamp method) of JIS K5600-7-8 was performed, and color difference ( ΔE) was measured.
The test results of Examples 1 and 2 and Comparative Examples 1 to 3 are shown in Table 1.

As shown in Table 1, the coating of the present invention, the initial temperature T ₁ and contamination after temperature T ₂ are both low, the difference between them was small. That is, the reflection performance of heat rays was high, and the reflection performance could be stably maintained. As described above, it was confirmed that by using the composite pigment M and the compound X in combination, good heat ray reflection performance and an effect of stably maintaining the reflection performance can be obtained.

  Moreover, the color difference in an accelerated weathering test was small, and there was little surface contamination. That is, the aesthetics were maintained over a long period.

On the other hand, in the example containing no composite pigments M (Comparative Example 1), the value of the initial temperature T ₁ is higher, the reflection performance of the heat ray is low. In addition, even in the case where the composite pigment M is contained, in the examples where the coating composition layer (B) is not formed (Comparative Examples 2 and 3), the color difference in the accelerated weather resistance test is large, and gloss reduction due to ultraviolet rays is observed. The aesthetics could not be maintained for a long time.

As described above, since the heat ray highly reflective coated product of the present invention uses the composite pigment M and the compound X in combination, the heat ray reflection performance is high, and the reflection performance can be stably maintained.
In the heat ray highly reflective coating of the present invention, the composite pigment M is contained in the coating composition layer (A) and the compound X is contained in the coating composition layer (B). Thus, since the composite pigment M is disposed in the lower layer and the compound X is disposed in the upper layer, the effect of preventing the contamination of the surface by the compound X is improved, and the surface aesthetics can be maintained over a long period.

Claims (10)

A coated article having a coating composition layer (A) and a coating composition layer (B) formed on the coating composition layer (A) on an object to be coated,
The coating composition layer (A) contains a composite metal oxide pigment containing an oxide of Bi and / or Y and an oxide of Mn, and a resin (a),
The coating composition layer (B) is represented by the general formula Si (OR) ₄ (wherein R may be the same as or different from each other, and represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). A heat ray highly reflective paint comprising a compound or a partial condensate thereof and a resin (b).   The heat ray highly reflective paint according to claim 1, wherein the coating composition layer (B) further contains an ultraviolet absorber.   The heat ray highly reflective coated article according to claim 1 or 2, wherein a part or all of the resin (a) and / or the resin (b) is a fluororesin.   The content of the composite metal oxide pigment contained in the coating composition layer (A) is 0.1% by mass or more based on the total amount of the composite metal oxide pigment and the resin (a). 3. A heat ray highly reflective paint according to any one of 3 above.   The heat ray highly reflective coated article according to any one of claims 1 to 4, wherein the coating composition layer (A) and / or the coating composition layer (B) further contains a curing agent. A composition (A1) containing a composite metal oxide pigment containing an oxide of Bi and / or Y and an oxide of Mn and a resin (a) is applied onto an object to be coated, and a coating composition layer ( A) is formed,
Next, on the coating composition layer (A), the general formula Si (OR) ₄ (wherein R may be the same as or different from each other, and represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). The coating composition layer (B) is formed by applying a composition (B1) containing a compound represented by the formula (1) or a partial condensate thereof, and a resin (b) to form a coating composition for heat ray high reflection. Method.   The coating method of the heat ray highly reflective coating according to claim 6, wherein the composition (B1) further contains an ultraviolet absorber.   The coating method of the heat ray highly reflective coating according to claim 6 or 7, wherein a part or all of the resin (a) and / or the resin (b) is a fluororesin.   The content of the composite metal oxide pigment contained in the composition (A1) is 0.1% by mass or more based on the total amount of the composite metal oxide pigment and the resin (a). A method for applying a heat-reflective coated object according to crab.   The coating method of the heat ray highly reflective coating according to any one of claims 6 to 9, wherein the composition (A1) and / or the composition (B1) further contains a curing agent.